Localised Corrosion: General Discussion : Faraday Discussions

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Cite this: DOI: 10.1039/c5fd90046h
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Localised corrosion: general discussion†

Gerald Frankel, Geoffrey Thornton, Steven Street, Trevor Rayment,
David Williams, Angus Cook, Alison Davenport, Simon Gibbon,
Dirk Engelberg, Cem Örnek, Arjan Mol, Philippe Marcus,
David Shoesmith, Clara Wren, Kirsi Yliniemi, Geraint Williams,
Published on 01 July 2015. Downloaded on 01/07/2015 16:00:38.
Stuart Lyon, Rob Lindsay, Trevor Hughes, Johannes Lützenkirchen,

Su-Ting Cheng, John Scully, Siaw Foon Lee, Roger Newman,
Christopher Taylor, Ross Springell, Janine Mauzeroll,
Sannakaisa Virtanen, Stephane Heurtault and James Sullivan
DOI: 10.1039/c5fd90046h
Philippe Marcus opened a general discussion of the paper by Roger Newman:

Should the passive lm not be signicantly involved in pit initiation (as you
suggest), how would you explain that the time to initiation is very much depen-
dent on the nature of the passive lm?
Roger Newman responded: I never said that the passive lm is not involved in
pit initiation. I understand (of course) that longer passivation gives a longer
induction time for pitting. What I say is that the effects of parameters like alloy
composition, environment composition, potential, and temperature, are not
easily accommodated (at least not predictively) within a passive lm breakdown
model, but fall out naturally from a modied Galvele type of model that uses
pitting potential data (or, if one has the time, lower extremes of pitting potential
distributions). Now I don't know whether or not the nest details of lm break-
down, detectable at the pA level or lower in electrochemical experiments (not nA
to mA – those are already pits), and/or on very pure, at alloy surfaces, follow the
same rules that we nd using pitting potentials on industrial or semi-industrial
alloys. Those measurements have not been done. Actually I don't think stainless
steel is necessarily the best model system for such studies. Under certain
conditions, as shown by Bardwell many years ago, iron shows blizzards of pits
that are clearly not impurity-particle-related; probably aluminum too. In stainless
steel we really don't know whether pit initiation ever occurs without a micro-
crevice and/or an impurity particle.
From the viewpoint of practical utility, the Galvele type of approach clearly has
the advantage. The Critical Pitting Temperature (CPT) is a propagation-related
transition below which metastable pits never become stable at any potential. My
group has published extensively on that. One can make a foolproof, if expensive,
† Electronic supplementary information (ESI) available: SVET scans movie. See DOI: 10.1039/c5fd90046h
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alloy selection by looking up CPT values for different alloys. Their resistance to
passive lm breakdown is wholly irrelevant so far as temperature effects are
concerned.
John Scully asked: Your paper discusses several important dissolution nuances
such as the way Fe and Ni dissolve during corrosion and how that is affected by
sulfur. Has our understanding advanced regarding how a nickel or iron atom
oxidizes given different rst and second nearest neighbor arrangements such as
in multi-element solid solutions?
Roger Newman replied: We are dealing here with what Pickering would have
called region 3 dealloying – that is, Ni enriches during simultaneous dissolution,
without (as far as we know) porosity formation. Some insights have been gained on
Pickering's region 1 dealloying (low potential, only one element dissolving – not
really accessible for FeNi) through work of Sieradzki and (for an initially ordered
alloy) Renner. Also, Erlebacher's MESOSIM simulation can change the “bond
energies” and examine the resulting kinetics and morphology.1–4 But simultaneous
dissolution is harder to study. Clearly Ni dissolution limits, in a way, the dissolution
of the whole alloy, and if the Ni dissolution is activated by S adsorption, then the
alloy will dissolve faster (of course Fe dissolution is also activated). Regarding the
effect of Ni content on this surface enrichment and its consequences, I don't believe
a systematic study has been done for the FeNi system, and surface analysis of dis-
solved or dissolving samples is a huge challenge. Obviously one doesn't get exactly
the same polarization curve for 5% Ni as for 50% Ni, and when I tried this (on a
small scale) I remember having problems with martensite at certain Ni content.
Experimentally, it would be nice if there was a binary alloy of more noble metals that
could be subjected to either simultaneous or selective dissolution depending on the
potential, with no interference from hydrogen evolution, but the usual Au alloys in
simple acids are not suitable for that, and many other systems have bad phase
diagrams. Possibly one could use a complexing solution like cyanide.
Many years ago we thought we had shown that porosity was formed during
simultaneous dissolution of FeNi in HCl solution, and we made a link with Cl-
SCC of stainless steels. I still believe that, although the papers were not very
convincing.5
1 H. W. Pickering, Corros. Sci., 1983, 23, 1107.

2 I. C. Oppenheim, D. J. Trevor, C. E. Chidsey, P. L. Trevor and K. Sieradzki, Science, 1991,
254, 687.
3 F. U. Renner, A. Stierle, H. Dosch, D. M. Kolb, T.-L. Lee and J. Zegenhagen, Nature, 2006,
439, 707.
4 J. Erlebacher, J. Electrochem. Soc., 2004, 151, C614.
5 R. C. Newman, R. R. Corderman and K. Sieradzki, Evidence for de-alloying of austenitic
stainless steels in simulated stress corrosion crack environments, Br. Corros. J., 1989, 24,
143–148.
Gerald Frankel said: Others have shown that the semiconducting properties on
the passive lm on Alloy 800 are a function of the thiosulfate concentration.1 This
behavior correlates with the pitting behavior. In a sense, your measurements are
also correlations. How can you rule out the impact of the passive lm?
1 J. Luo, personal communication.
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Roger Newman responded: I don't know what is meant by correlation in the
case of the semiconducting properties. I have seen work of this type where thio-
sulfate was used, but as I recall (and it may not have been the work of Luo), the
authors ignored the framework that we set out in the 1980s. There are many
elements of that framework, but the two most important ones are (1) that pitting
occurs (with chloride and thiosulfate) at potentials way below where it would ever
occur with only chloride, and (2) that pitting occurs in mixtures of sulfate and
thiosulfate, but would never occur, at any potential, with only sulfate. I don't know
how a “correlation” based on semiconductor properties can accommodate either
of these observations, which it would need to do to make any progress at all.
Philippe Marcus asked: Do you have any direct evidence that pitting can be
initiated with sulfate/thiosulfate without chlorides (or is scratching necessary to
depassivate the surface)? In work we did on FeCr alloys1 we showed that when
both chlorides and thiosulfates are present, passivity breakdown is caused by
chlorides and then repassivation is precluded by adsorption of sulphur.
1 C. Duret-Thual, D. Costa, W. P. Yang and P. Marcus, The role of thiosulfates in the pitting
corrosion of Fe-17Cr alloys in neutral chloride solution: Electrochemical and XPS study,
Corros. Sci., 1997, 39, 913–933.
Roger Newman replied: It does initiate eventually if you just leave the sample
in the susceptible range of potential – that's one reason why we apply an initial
passivation in pure sulfate solution (the other reason is that we want a nice low
baseline current when we scratch). It does take longer to initiate than when we
have thiosulfate and chloride, which can be studied using ordinary voltamme-
try.1To study the sulfate–thiosulfate pitting using voltammetry requires an
extremely low scan rate.
I would emphasize (and this is very important) that sulfate–thiosulfate pitting
occurs at potentials that are far lower than where ordinary chloride pitting occurs.
Of course we don't know how much of the above is affected by particulate in
the alloy, or surface roughness. It may be useful to compare the chloride–thio-
sulfate and sulfate–thiosulfate systems using very clean alloys, to see if the
difference in initiation rate between chloride and sulfate increases. Choice of
surface nish(es) would be important in such experiments. It is possible that the
sulfate–thiosulfate pitting (or for that matter chloride–thiosulfate pitting) may
vanish on surfaces that are extremely smooth and particle-free (see my response
to Trevor Rayment for a comment on sputtered thin lms and the absence of
pitting above a certain Cr content).
1 R. C. Newman, H. S. Isaacs and B. Alman, Effects of sulfur compounds on the pitting

behaviour of type 304 stainless steel in near neutral chloride solutions, Corrosion, 1982,
38, 261–265.
Dirk Engelberg asked: I've noticed that all tested microstructures were in the
solution annealed condition, which is different to how these alloys are used in
plant (e.g. thermally treated – TT). Would you expect an effect of microstructure
on pit nucleation behaviour and frequency? For example, how would the presence
of carbides change the lower/upper bounds of pitting in Table 3/Figure 4?

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Roger Newman answered: We use solution annealed alloys because we don't
want to be distracted by microstructure effects – our interest is in the solid
solution. Regarding the TT treatment, I recall we did a few experiments where we
found easier pitting, probably because the Cr depletion is not completely elimi-
nated –perhaps the Cr level next to the grain boundary is still 1 or 2% below the
bulk alloy. It might be interesting to pursue that further. For mill-annealed alloys
the depletion may be less. But certainly one should pay attention to microstruc-
ture in any such study dealing with real plant experience, as we sometimes do – in
Canada we still have steam generators with Alloy 600 tubing that is sensitized.
One way to preserve that tubing is to reduce secondary-side exposure to oxygen-
ated water during plant outages, as that can contain reduced sulfur species from
sludge.
Trevor Rayment commented: This is a question for Roger Newman and Phil-
ippe Marcus.
There has been a long standing debate in the corrosion community concerning
the mechanism by which molybdenum confers protection against pitting. A
simple, if not simplistic, summary of the two schools of thought is a follows. The
rst school (Philippe Marcus) proposes that the role of Mo is to make the passive
lm more resistant to pitting, whereas the second school (Roger Newman)
proposes that the role of Mo is upon dissolution kinetics aer initiation of pitting
has taken place.
The debate over the mechanism(s) of pitting protection of molybdenum is not
resolved but there has been no discussion of this important topic within this
meeting yet. A great deal of experimental data has been published but it does not
seem to have convinced all parties to the discussion. A Faraday meeting presents
an ideal forum for such a debate.
Therefore I would like to ask Roger and Philippe to propose experimental
evidence (new experiments) that others could provide which would persuade
them to change their mind on the mechanism for molybdenum protection in
corrosion.
Roger Newman answered: I believe many of the critical experiments have been
done already. The problem, from where I stand, is that a long list of phenomena
in pitting are nicely accounted for (and in several cases quantitatively) by a
modied Galvele type of model.1 Similar success was achieved in studies that
addressed the effects of bromide, thiosulfate, temperature, etc. The only thing
missing from this long list of successes is that (almost always) our denition of
pitting was stable pitting. If one's denition is “rst onset of detectable current
transients due to passive lm breakdown,” then indeed there is some evidence
that thiosulfate takes advantage of spontaneous breakdown events, detectable at
the nA level in pitting experiments. But these (perhaps chloride-induced) events
are still pits – quite large actually. Burstein and his students looked down to the
pA level and found what they considered to be a different type of event, due
perhaps to salt forming under the passive lm and bursting it open.2 I don't recall
whether the frequency and potential dependence of such events was compared in
steels with and without Mo. Such data (although the charges under the transients
were still substantial in terms of number of atoms dissolved) may be valuable in
determining whether or not Mo affects the nucleation frequency of relevant

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events. I also don't know whether or not the Burstein type of event occurs, or
occurs with different frequency, in steels with lower particulate content than
commercial steels. Such delicate experiments have not been done, as far as
I know, in support of the “passive lm breakdown” hypothesis.
One observation that may address whether the passive lm controls pit initi-
ation was that of Ryan et al.3 Pitting vanished above a critical Cr content of the
alloy, even under very aggressive conditions. However our interpretation was as
follows – these alloys were very smooth, and extreme current densities would be
required to initiate any kind of pit. However below the critical Cr concentration,
initial dissolution proceeded into the alloy along Fe-rich paths, creating the
necessary occlusion for pit nucleation and bringing the observations back into the
“Galvele” fold.
The sulfate–thiosulfate pitting is addressed in my response to Dr Marcus. One
issue here is that we do not know whether the pitting that we studied
(in commercial or home-made alloys) was related to second-phase particles.
1 N. J. Laycock and R. C. Newman, Localized dissolution kinetics, salt lms and pitting
potentials, Corros. Sci., 1997, 39, 1771–1790.
2 S. P. Mattin and G. T. Burstein, Philos. Mag. Lett., 1997, 76, 341.
3 M. P. Ryan, N. J. Laycock, R. C. Newman and H. S. Isaacs, The pitting behavior of Fe–Cr
thin lm alloys in hydrochloric acid, J. Electrochem. Soc., 1998, 145, 1566–1571.
Philippe Marcus answered: My response to this question is in three points:

(1) Role of the passive lm in protection against pitting.
The role of the passive lm in preventing or retarding pitting initiation is
extremely important. Indeed it has been demonstrated that on the same alloy and
in the same solution enhanced pitting protection is obtained by ageing in the
solution, and that this is related to modications of the chemical composition of
the passive lm.1
An experiment that could contradict the above observation and conclusion
would be an experiment in which a well controlled change of composition and
structure of the passive lm produced on the same alloy and in the same solution
would change nothing in the pitting initiation (pitting potential and time to
initiation).
(2) Role of molybdenum in both pitting protection by a passive lm containing
molybdenum, and dissolution kinetics aer pitting initiation.
There is no reason to exclude that molybdenum plays both roles, and indeed I
think that Mo has two effects: it acts in the passive lm resistance against pitting
initiation, as well as in the dissolution kinetics aer initiation of pitting.
The former effect is likely provided by Mo6+ locally enriched on the passivated
surface2 and the latter effect is provided by Mo in the alloy slowing down the
dissolution kinetics in the active state (an effect clearly observed in comparing the
dissolution kinetics in the active state of 304 and 316 stainless steels, or ferritic
stainless steels without and with molybdenum, see e.g. Marcus and Oleord.3
(3) Another benecial effect of molybdenum, originally shown for nickel
alloys,4 is that Mo located on the surface binds to adsorbed sulfur and removes it
from the surface (by dissolution), thus improving the corrosion resistance when
sulfur species are present.

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1 W. P. Yang, D. Costa and P. Marcus, Chemical composition, chemical states, and resis-
tance to localized corrosion of passive lms on an Fe–17%Cr alloy, J. Electrochem. Soc.,
1994, 141, 111–116.
2 Vincent Maurice, Hao Peng, Lorena H. Klein, Antoine Seyeux, Sandrine Zanna and Phil-
ippe Marcus, Faraday Discuss., 2015, DOI:10.1039/c4fd00231h.
3 P. Marcus and I. Oleord, A round robin on combined electrochemical and AES/ESCA
characterization of the passive lms on Fe–Cr and Fe–Cr–Mo alloys, Corrosion Science,
1988, 28, 589–602.
4 P. Marcus and M. Moscatelli, The role of alloyed molybdenum in the dissolution and the
passivation of nickel–molybdenum alloys in the presence of adsorbed sulphur, J. Elec-
trochem. Soc., 1989, 136, 1634–1637.
John Scully enquired: Operating on the assumption that the pitting potential
reects ease of initiation and stabilization with perhaps more weight on stabili-
zation, are there examples where the oxide plays a big role in initiation and
thereby affects the pitting potential? In relatively defect free materials, could
emphasis shi towards the oxide? One observation has been in the case of
amorphous glasses and high purity or relatively defect free stainless steels that
there are very few initiation events detected at the instrument limit. These alloys
enjoy very high pitting potentials and it seems that the rst “detected pit”
immediately stabilizes pitting. This stands in contrast to garden variety stainless
steels and aluminum alloys with many inclusions and intermetallics where there
are many initiation events. You have mentioned that if the defect is on the order
of the oxide thickness then stabilization would require extraordinary anodic
currents and I agree. But, what was the atomistic event that led to rupture of the
oxide in the rst place and is oxide engineering then a fruitful avenue for research
in relatively defect free materials?
Roger Newman answered: My main point is that the standard of proof is very
high if one wants to attribute an improvement in pitting resistance (by alloying) to
an increased resistance to passive lm breakdown, other parameters such as
surface nish and inclusion population, nature and size being kept constant.
I don't know of any instance where that standard has been met, whereas for
“dirty” alloys, the Galvele type of approach meets it routinely. You are asking
whether for clean and/or specially formulated alloys the lm might start to
dominate and could be engineered for resistance to breakdown. One response to
that would be to note that if pitting is not eliminated completely, the pits that do
initiate will grow rapidly – this is like “dangerous” inhibition. That is why I would
prefer to see passive lms engineered to reduce the rate of the cathodic reaction –
this is like “safe” inhibition. Assuming that in some applications the oxide could
be appropriately engineered on a very clean and smooth substrate (and one would
have to consider joining of the material, oxidation, surface damage, surface
cleanliness, plastic deformation, etc.), I have no doubt that the nucleation
frequency of pitting could be kept very low. We saw that ourselves in stainless
steel thin lms prepared by ion-assisted ion-beam sputtering (see Ryan citation in
another answer). Of course that is a kind of coating, so one might more logically
see improvement via the oxide route as something to pursue using advanced
vacuum coating technology applicable to large components. As you know, such
considerations apply differently to iron-base and aluminum-base systems, so
there is no commonality across the range of our usual materials that suffer from
pitting. It has been shown that thin-lm aluminum contaminated by oxygen has

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very high pitting resistance1 – one might consider this to be some kind of lm-
reinforcement effect, but I personally consider that this oxygen-alloying effect can
be accommodated within a reaction-transport type of picture wherein oxygen
dissolution into a proto-pit consumes acid.
1 G. S. Frankel et al., J. Electrochem. Soc., 2014, 161(4), C195–C200.
Dirk Engelberg opened a general discussion of the paper by Steven Street: For
your time-lapse imaging experiment (Fig. 4) do you expect a change in relative
humidity over time? Do you take the sample out of the humidity cabinet, and is
there then enough time to equilibrate the environment before you take the next
images?
Steven Street replied: Samples were in humidity controlled desiccators with

clear glass lids through which observations can be made, so there was no expo-
sure to the lab atmosphere during measurements. The time taken to take the
image was about 1 min, and the contents of the desiccator helped buffer the
temperature so there was little variation here. A Lascar data logger collecting both
RH and temperature shows no substantial change in either during optical
measurements, maintaining temperature within 3 C and RH within 3%.
Geraint Williams asked: What role does differential aeration play in the pitting
corrosion of the 304 observed under a magnesium chloride containing water
droplet? For example, if the surface were to be fully immersed in an aqueous
solution of equivalent concentration, would spontaneous pitting still be observed.
Is there a lower threshold magnesium chloride concentration observed under a
droplet for spontaneous pitting in the absence of external polarisation, than when
the surface is fully immersed?
Is there any evidence that local alkalinity at the circumference of the droplet
causes precipitation of magnesium hydroxide in the region? Maybe this would
explain the ring of apparent metal excavation at the periphery of the droplet as
shown in Fig. 4.
Finally, for droplets of different sizes, but xed concentration, what parameter
controls the rate of anodic dissolution? If the pit growth rate is a function of the
area of solution in contact with the metal then this would indicate surface/
cathodic control rather than there being any ohmic constraints.
Steven Street responded: As noted in another response, the fact that pits do not
grow only in the centre of the droplets suggests that the entire surface is
vulnerable to pitting initiation in thin droplets. We have started exploratory
comparisons with full immersion experiments and have found pitting in
concentrations similar to those maintained at the RH used in our atmospheric
experiments. This work is in ongoing. Local alkalinity is thought to cause the
precipitation of Mg(OH)2 and possibly MgCO3, pinning the droplet perimeter.1
Figure 4 shows the perimeter of the pit, not the droplet, so we would expect the
solution still be to quite acidic here. For xed CDD and RH (concentration),
increasing the droplet diameter tends to give a larger shallow dish diameter, as
noted in another answer, so it is likely that this effect is due to the increasing area
available for the cathode reaction. Similar increases with droplet size were

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2
observed by Mi et al. Increasing CDD (i.e. droplet height) while maintaining
droplet area and concentration also increases the corrosion rate (Fig. 3), which we
believe is IR drop related, as discussed in the paper.
1 T. Tsuru, K. Tamiya, and A. Nishikata, Formation and growth of micro-droplets during the
initial stage of atmospheric corrosion, Electrochim. Acta, 2004, 49, 2709–2715.
2 N. Mi, S. M. Ghahari, T. Rayment and A. J. Davenport, Use of inkjet printing to deposit
magnesium chloride salt patterns for investigation of atmospheric corrosion of 304
stainless steel, Corros. Sci. 2011, 53, 3114–3121.
Gerald Frankel asked: In our work on corrosion of SS under droplets at low RH,
the shallow pits smoothly transitioned into attack at smaller areas we called ears,
which we attributed to cathodic limitations.1 Why is that not a good explanation
for your observations of pit morphology change?
1 Bastian Maier and G. S. Frankel, Pitting corrosion of bare stainless steel 304 under chloride
solution droplets, J. Electrochem. Soc., 2010, 157, C302–C312.
Steven Street answered: The spiral shaped pits in this work are caused by the
“earing” mechanism you described, and this should indeed have been claried.
We agree that the role solution thickness and cathodic current limitation is
crucial to the development of these pits, which is supported by our observations
of the effects CDD and conductivity (RH). We extended this approach to include
the role of mass transport limitation, as we believe this is necessary in explaining
the formation of satellite pits. It is interesting that you did not observe satellite
pits, possibly due to a combination of slightly higher CDD and ner grinding of
the metal surface, which would have removed occluded initiation sites that in our
work led to satellites.
Dirk Engelberg asked: Is there interaction between satellite pits and the
shallow dish/pit region, since the shallow region seems to have grown into
satellite pits (e.g. Fig. 3 and Fig. 4)? (how does this affect cathodic vs. anodic
regions?)
Steven Street answered: Evans’ Droplet experiments on steel describe macro-

scopic general corrosion attack, not localised pitting corrosion. As such, they do
not account for microstructure or inclusions common in stainless steel alloys. As
Roger Newman pointed out, the model works on the basis of differential aeration
which preferentially supplies edges of droplets with oxygen and promotes
cathodic reactions there. The observation that usually only one pit is seen in a
droplet is expected to be due to the drop in potential in the system associated with
pitting. Under full immersion conditions, it is common to observe a sequence of
metastable pits that show recovery of the potential aer repassivation of previous
pits.
David Williams said: I wonder about the temporal sequence of events in your
experiments. Could it be that the shallow dishes form as a consequence of the
activation of the surface near a pit by corrosion products (specically suldes or
thiosulfates) that are diffusing out of an active pit? Such effects have been shown
before.1

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1 D. E. Williams, T. F. Mohiuddin, Y. Y. Zhu, Elucidation of a trigger mechanism for pitting
corrosion of stainless steels using submicron resolution scanning electrochemical and
photoelectrochemical microscopy, J. Electrochem. Soc., 1998, 145, 2664–2672.
Steven Street responded: We don’t doubt the importance of sulphide inclu-

sions in pit initiation in these alloys, and there is a rich literature that supports
this. In the discussion section of the paper we suggest that this is not the only
factor controlling dish diameter since this varies with position in the droplet. In
unpublished work, large droplets of 10 ml have consistently larger shallow dish
regions with diameters exceeding 350 mm, and 100 ml droplets with shallow dishes
of over 800 mm diameter. If sulphide is the controlling factor we would expect a
small variation in dish sizes more similar to each other.
Cem Örnek commented: In 304L austenitic stainless steel the delta ferrite
content is about 6–14%, depending on the microstructure processing orientation
(TD, RD, ND). The ferrite has signicantly different chemical composition in
contrast to the austenite matrix which questions the role in localised corrosion.
Furthermore, there are MnS and other non-metallic inclusions oen present in
the microstructure. How are these related to the corrosion morphology during
atmospheric corrosion? Are there any preferential initiation sites observed? Can
we say from selective corrosion? Can we speak about pitting corrosion if we see
odd shaped corrosion morphologies?
Steven Street responded: Our steel contains ~4% delta ferrite, most of which is
below the plate surface. We have demonstrated that it inuences pit propaga-
tion.1 Our steel also contains sulphide and oxide inclusions which are known to
be pit initiation sites. However we have not carried out a systematic study on the
inuence of different initiation sites.
1 A. J. Davenport, L. Guo, N. Mi, H. Mohammed-Ali, S. M. Ghahari, S. R. Street, N. J. Laycock,

T. Rayment, C. Reinhard, C. Padovani and D. Krouse, Mechanistic studies of atmospheric
pitting corrosion of stainless steel for ILW containers, Corros. Eng., Sci. Technol., 2014, 49,
514–520.
Cem Örnek asked: Evans introduced the atmospheric corrosion model under
thin-lm electrolytes formed by a hemispherical water droplet. Thus the anode is
primarily located in the centre of the droplet due to rapid oxygen depletion and
impeded oxygen supply and the periphery of the droplet forms the cathode due to
the excessive and quick access of oxygen. Preferential corrosion would be
expected to occur at or close to the centre due to the development of a large net
anodic potential. However, the results shown (and the poster from Angus Cook,
University of Birmingham) clearly contradict the model of Evans. Research on the
atmospheric corrosion behaviour on the same material and on 2205 duplex
stainless steel by my humble self can conrm your observed results. However,
there is no clear explanation given as to why the corrosion initiation occurs mostly
between the centre and the peripheral area of a hemispherical chloride-con-
taining droplet. Furthermore, the initiation of corrosion is concentrated on a
conned region, and, usually, only one or a few corrosion pits are observed which
is signicantly different to corrosion initiation sites under immersed conditions.

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Is there an explanation for this? By the way, corrosion was also observed occurring
on the peripheral area and also on secondarily spread chloride regions.
Roger Newman replied: I don't believe the situation is as tidy as the Evans
experiment. There are two major differences. First, the stainless steel is spontane-
ously passive, while the iron is spontaneously active. In the Evans experiment it is
the alkalization at the periphery of the drop that passivates the iron and creates the
active–passive couple. In the stainless steel experiment there is pit initiation and
propagation, which is very different. Second, oxygen reduction on stainless steel is
normally activation controlled, except where the stainless steel is in the active state,
while in the Evans experiment oxygen reduction is diffusion-limited. As I indicated
in another answer, oxygen reduction on stainless steel can also show apparent
“limiting current densities” that are too low to be diffusion-limited in the electrolyte.
Roger Newman commented: The reference to Evans' famous drop experiment

(on iron) may not be appropriate if oxygen reduction on stainless steel is kineti-
cally rather than diffusion limited. In the drop experiment, oxygen reduction is
everywhere under diffusion control.
As a footnote to this comment, it might be interesting to vary the partial
pressure of oxygen over the experiment, or in some other way to probe the status
of the oxygen reduction reaction.
An old observation is that oxygen reduction on stainless steel sometimes
appears to be mass transfer limited, but the limiting current density is too low for
boundary-layer diffusion. In that case something within the passive lm itself is
limiting the reaction. Someone must have explained this.
Steven Street answered: Thank you for your very interesting comments. A
further brief discussion on Evans’ droplet model has been addressed in answer to
another question.
Dirk Engelberg asked: Can you suggest a viable corrosion mitigation strategy to
prevent localised corrosion in this system (since you show pitting corrosion occurs
with exposure to deliquescence relative humidity, and increasing the relative
humidity (e.g. 56%) also results in pitting corrosion). Do you accept a chloride
deposition density of 10 mm cm2 as a working threshold or have you observed
corrosion occurring below this threshold? Can you speculate whether a change of
shape during pit growth can be used to affect (and control) pit growth kinetics?
Steven Street responded: The obvious solution is to try to keep chloride concen-
trations as low as possible and to limit the thickness and continuity of the electrolyte
layer. An alternative method would be maintaining a very high RH in storage, to
ensure any salts that do deliquesce remain dilute, but these would necessarily pass
through an initial highly concentrated stage which may cause corrosion, if only
supercially. As initiation sites are seen to not reinitiate pitting once passivated,
natural wet–dry uctuations could be used to exhaust these sites on the surface of the
alloy.1 An improved alloy, such as 316L, would certainly improve performance. 10 mm
cm2 CDD is signicantly lower than the values used in this paper. A recent study2
suggests that there is merit to the use of a working threshold.

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1 A. J. Davenport, L. Guo, N. Mi, H. Mohammed-Ali, S. M. Ghahari, S. R. Street, N. J. Laycock,
T. Rayment, C. Reinhard, C. Padovani and D. Krouse, Mechanistic studies of atmospheric
pitting corrosion of stainless steel for ILW containers, Corros. Eng., Sci. Technol., 2014, 49,
514–520.
2 C. Padovani, R. J. Winsley, N. R. Smart, P. A. H. Fennell, C. Harris and K. Christie,
Corrosion control of stainless steels in indoor atmospheres? Practical experience (Part 2),
Corrosion, 2015, 71, 646–666.
David Williams asked: I wonder if there are any convection effects associated
with surface tension gradients developed as droplets evaporate? Thus, are there
any effects that are different at the centre compared with towards the edge of the
droplet?
Steven Street replied: Convection effects are something we did not consider
and perhaps should have, as the droplet loses up to 95% of its initial volume as it
equilibrates with RH within the rst hour. We show in Figure 8 that the diameter
of the shallow dishes are greater in the centre of the droplet. We attribute this to
an increased IR drop and mass transport limitations at the edges. We do not
observe any other effect that might be attributed to convection.
Siaw Foon Lee communicated: Under the section of “Experimental”, third

paragraph – Arrays of 2 ml droplets of 0.27 M MgCl2 were deposited.and Fig. 1(a)
showing the relationship between the solution concentration (M) of MgCl2 and
relative humidity (%). My question is that could the author shows the calculation
steps of how to convert 2 ml droplets of 0.27 M MgCl2 to 5M MgCl2 aer it was held
in an ECO135 atmospheric chamber for 24 h with the humidity of 33%?
Steven Street communicated in reply: The concentration of the solution is

determined by its water activity as it reaches equilibrium with the relative
humidity. At equilibrium, the water activity in the air and water phases are equal,
regardless of the initial solution concentration. The calculations of equilibrium
concentrations are based on Figure 1(a) which was calculated using OLI Systems.
Siaw Foon Lee communicated: Table 2 – the humidity of 33% has a droplet
area on deposition of 0.048 cm2 and has an average droplet CDD of 80 mg cm2.
The humidity of 43% has a droplet area on deposition of 0.048 cm2 that is same as
that of the humidity of 33%, however, it has an average droplet CDD of 790 mg
cm2. I am curious to know how the author works out the calculation since this
topic is new to me.
Steven Street communicated in reply: Chloride deposition density is an

average measure of mass of chloride over a dened area, in this case the area of
the droplet. In our experiments, CDD was altered by varying the deposition
solution concentration. As noted in the paper (Table 2) the droplet areas are
measured at deposition, as droplet spreading can occur during atmospheric
corrosion.
Siaw Foon Lee communicated: Under the section of “Experimental,” subsec-

tion of “Electrochemical sweeps,” second paragraph, starting from the second
line. The solutions used were de-aerated by bubbling argon for 20 min.” Could I

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know about the minimum oxygen concentration of the electrolyte the author
achieved using this method? Can the oxygen concentration remain the same
during the experiment using this method?
Steven Street communicated in reply: Oxygen concentration was not measured

in this experiment. Checks on similar measurements on oxygen reduction rate on
Pt wire suggest that this method can maintain concentration.
Dirk Engelberg opened a general discussion of the paper by V. Vivier: Do you

keep your micro-capillary very close to the surface (10–15 microns) to initially
generate a “crevice-type” environment to induce pitting (crevice)? Do you try to
keep the condition (in particular the chloride concentration) in this conned
space below the capillary stable during the experiments?
Stephane Heurtault answered: The proximity of the micro-capillary to the

stainless steel surface, together with the chosen chloride concentration in the
syringe and the release ow rate, helps to create an appropriate environment for
pit initiation and propagation. The distance between the micro-capillary and the
stainless steel surface was selected to produce a single pit on the steel. 15 microns
is the highest distance fullling this condition. The chloride concentration
injected by the micro-capillary does not necessarily have to be constant during the
propagation phase. The supply of chloride has only to be greater or equal to the
critical chloride concentration determined in part 3.3.2 of this article.
As you mention crevices, it is well known from the literature that crevices can
develop from pits. However aer 1 h of propagation, a pit cross section performed
in our pit did not show any crevice.
Alison Davenport remarked: Have you carried out a systematic investigation to

determine whether the ow rate of the solution inuences pit growth? Some of
your pits appear to have broken covers: were they damaged during the experiment
or aerwards during transfer to the SEM?
Stephane Heurtault replied: The ow rate of the solution is one of the main
parameters for the supply of chloride in the environment and it inuences the pit
growth. The supply of chloride (in mol h1) can be dened as the product of
chloride concentration (in mol L1) and ow rate (in L h1). However, we have
shown that we can control the amount of chloride independently by changing the
chloride concentration or by modifying the ow rate (see for instance the results
presented in Fig. 5). With a chloride ow rate of 5.4 mL h1 (as used in most of our
experiments presented in this paper) and taking into account the evolution of the
pit volume plotted in Fig. 10, only 3 min are required to renew entirely the pit
solution aer 1 h of propagation, and it will take 30 min aer 10 h of propagation.
Thus, the convection induced by the micro-capillary may be an important factor
that controls the pit propagation. To avoid such a behavior, it is possible to
generate and to propagate the pit in two successive steps: rst, the pit is generated
beneath the micro-capillary and then, it is sustained by controlling the bulk
concentration in chloride as was shown possible in the last part of the article.
We believe that the pit cover shown in Fig. 6(a) was not damaged during the
experiment but aerwards during transfer to the SEM. Indeed, in another

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experiment, we succeeded in obtaining a no-broken pit cover using the same
experimental conditions. Nevertheless it is possible to break the pit cover during
the experiment, for example performing an anodic potential change during the
propagation.
Roger Newman asked: Why do you use such a strong sulfate solution? It seems
that complications from the mixing of chloride and sulfate could be minimized if
you just reduced the sulfate concentration by a factor of 10. Some of your
experiments where you vary the chloride might be affected by varying degrees of
inhibition by sulfate (since inhibition is related to the chloride/sulfate ratio).
Stephane Heurtault replied: We used such a strong sulfate concentration to be

sure that the solution conductivity is high enough, but we know that it affects the
pit growth. In our previous work,1 differences between sulfate and perchlorate
solution were investigated. Moreover, some experiments were performed using 6
M SO42 and 1.2 M Cl instead of 0.5 M SO42 and 1.2 M Cl. With this increase in
sulfate concentration (corresponding to a decrease of the chloride to sulfate
ratio), the inhibitor role of sulfate was shown. We agree with this comment that
the chloride to sulfate ratio is an important point instead of only indicating the
chloride concentration.
1 N. Aouina et al., Electrochim. Acta, 2013, 104, 274.
Gerald Frankel stated: You show that the depth varies with t0.5, which would
also be found for ohmic control. How can you rule out ohmic effects?
Stephane Heurtault answered: Indeed it should have been mentioned that the
variation of pit depth with t0.5 also accounts for ohmic control as shown previ-
ously.1 The same dependence with time of pit depth for both ohmic control and
diffusion complicates the data interpretation. However for a pit under diffusion
control, potential variation has no effect on the pit growth rate, whereas a pit
growing under ohmic control depends on potential according Ohm’s law. Addi-
tional experiments at 20 C injecting 3 M NaCl + 0.5 M H2SO4 with the glass micro-
capillary were performed by changing the electrode potential during the pit
propagation (data not shown in this paper). The single pit was initially formed at
0 V/MSE. Aer 1 h of propagation, the potential was changed to 0.4 V/MSE. Then
the pit depth with this modication of potential was measured and the current
density at the pit bottom aer changing the potential was calculated using
equation (5). It was shown that the modication of potential does not affect the
calculated pit bottom current density, indicating a diffusion-control process.
1 G. S. Frankel, J. Electrochem. Soc., 1998, 145, 2186.
David Williams commented Laycock et al. have given a rather complete

computational model for evolution of pit shape, including the perforated
covers.1,2 Have you been able to compare your results with such a model? Also,
have you been able to see the current uctuations that should result as the
perforations in the pit cover develop? Pit ‘death' happens when the cover is
detached and the internal processes cannot sustain the critical solution

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composition against the resultant increased ux out of the pit. This is usually
indicated by a sharp increase of current followed by an immediate fall to zero (e.g.
ref. 3). Have you been able to see such effects in your experiments?
1 N. J. Laycock, S. P. White, J. S. Noh, P. T. Wilson and R. C. Newman, Perforated covers for

propagating pits, J. Electrochem. Soc., 1998, 145, 1101–1108.
2 N. J. Laycock and S. P. White, Computer simulation of single pit propagation in stainless
steel under potentiostatic control, J. Electrochem. Soc., 2001, 148, B264–B275.
3 D. E. Williams, J. Stewart and P. H. Balkwill, The nucleation, growth and stability of
micropits in stainless steel, Corros. Sci., 1994, 36, 1213–1235.
Stephane Heurtault responded: The Laycock model is a great advancement in

our understanding of pitting propagation on stainless steel. This model was
devised for a disc-shaped pit and accounted for the presence of a salt lm at the
pit bottom. Due to this salt lm, an additional potential drop at the pit bottom
exists, which implies a lower current density beneath the salt lm than at the pit
edges. These results are fully consistent with our experiments (disc-shaped pit
and salt lm at the bottom of the pit). The Laycock model also accounts for the
presence of a pit cover, which is composed of a central hole surrounded by many
small perforations forming the lacy-like structure. According to the model, the
cover entirely dissolves for long-term pit propagation. In our experiments, using
the adequate chloride concentration injected by the micro-capillary, we can get
single pits which propagate without any pit cover (this is possible according to the
Laycock model) or we can also observe the propagation of a single pit with cover.
However, the pit cover obtained in our experiments has only a central hole at the
location corresponding to the chloride solution injection by the micro-capillary,
and only one or two perforations can be observed in the periphery. This specic
behavior may be explained by the presence of the micro-capillary above the pit
maintaining the concentration of chloride ions at a high level. We didn’t see any
current uctuations resulting from the perforations of the pit cover. This was
conrmed by SEM observations. However for both covered and uncovered pits, we
noticed small current oscillations which can probably be ascribed to the growth
and the breakdown of a thin oxide layer under the salt lm.1,2
Once the pit propagates, we have never observed repassivation aer the
collapse of the pit cover. However, it should be mentioned that an increase of the
electrode potential during the pit propagation was accompanied by the collapse of
the pit cover. In that case, the current increased sharply during the collapse, but
the propagation was maintained.
1 R. C. Newman and M. A. A. Ajjawi, Corros. Sci., 1986, 26, 1057.

2 N. J. Laycock and R. C. Newman, Mater. Sci. Forum, 1995, 192, 649.
Alison Davenport commented: We have recently carried out some radiography

work on the growth of 2D pits in stainless steel foils.1,2 We also found out that
growth rate at the bottom of the pit is slower than the sides of the pit. We also
attribute this to diffusion-controlled growth of the pit bottom. However, in the
presence of a perforated pit cover, the solution concentration at the pit mouth will
not be zero as the cover provides an additional diffusion barrier. We found that
the growth of the pit width is under ohmic control as the rate increases with
solution conductivity.

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1 M. Ghahari, In Situ Synchrotron X-Ray Characterisation and Modelling of Pitting Corro-
sion of Stainless Steel, PhD Thesis, University of Birmingham, 2012, http://
etheses.bham.ac.uk/3269/11/Ghahari12PhD.pdf.
2 M. Ghahari et al., Corros. Sci., submitted.
Alison Davenport opened a general discussion of the paper by David Shoe-

smith: What are the most effective ways to simulate the effect of radiation on
corrosion of UO2 under realistic conditions?
David Shoesmith answered: A number of experimental approaches can be

used.
(a) For g-radiolysis, direct exposure of the UO2 to a gamma eld with a cali-
brated dose rate can be used.
(b) For a-radiolysis, UO2 specimens doped with a-emitters (e.g., Pu(239),
U(233)) to provide a known dose rate have been used.1 This method provides an in
situ a-radiation eld.
(c) An alternative method for a-radiolysis is to use a thin layer electrochemical
cell with the electrode (UO2) brought close to a Au-coated a-source (G 25mm) with
a known dose rate.2 This method provides an ex-situ source.
(d) Intense beams (e.g., X-rays (Ross Springell et al.3)) can be used, but usually
produce extremely high dose rates well beyond those expected inside a failed
container.
(e) The inuence of g-radiolysis (and also a-radiolysis) can be simulated by
adding the anticipated concentration of hydrogen peroxide chemically. Evidence
in support of this approach is well documented.4
1 M. Broczkowski et al., ACS Symposium Proc., 2010, 1046, 34–380.

2 J. C. Wren et al., J. Electrochem. Soc., 2005, 152, B470–B481.
3 Ross Springell, Sophie Rennie, Leila Costelle, James Darnbrough, Camilla Stitt, Elizabeth
Cocklin, Chris Lucas, Robert Burrows, Howard Sims, Didier Wermeille, Jonathan Rawle,
Chris Nicklin, William Nuttall, Thomas Scott and Gerard Lander, Faraday Discuss., 2015,
DOI:10.1039/c4fd00254g.
4 J. C.Wren, ACS Symposium Proc., 2010, 1046, 271–295.
Ross Springell replied: Simulating the effects of corrosion of UO2 under real-
istic conditions initially requires one to dene what these conditions might be,
and this can depend on what scenario you choose. The most frequently used
method is the addition of small quantities of H2O2 to the aqueous environment.
This is based on the assumption that any container of spent nuclear fuel will likely
fail aer the rst few hundred years when the gamma elds from the ssion
products have decayed and the dominant radiation elds are driven by alpha
decay; in this case the dominant radiolytic product will be H2O2. However, the
most likely cause of any containment failure is due to potential defects in the
vessel weld. This will be present from day 1 and it is possible that water may
ingress way before all of the ssion products have decayed. In this instance,
strong gamma elds will also be present and this will result in both H2O2 and
other more oxidising free radicals at the fuel surface. A lot of this discussion really
depends on the precise packaging methods and eventual repository conditions.
One method to better simulate the radiation elds would be to study changes in
the UO2/water interfaces exposed to an alpha source and a gamma source, but
these would have to be ex-situ studies with characterisation of the structure with

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X-rays at a later time. The advantage of the experimental method outlined in this
paper is that we are able to probe the structural changes in situ.
John Scully asked: Could you comment on the number of adjustable or

disposable parameters that a model like this has, or should be limited to? Of
course, it seems that corrosion science might work to dene as many “unit
processes” as possible so as to eliminate some adjustable parameters when they
can be replaced. Is this your view too, or do you see another way forward?
David Shoesmith answered: The primary basis of a model like this one (fuel
corrosion model) is a mechanistic understanding of the key reactions required to
describe the corrosion process. Our guiding principle is that the model should
contain the minimum number of reactions necessary to reasonably represent the
overall process. To achieve this the model should contain the minimum number
of adjustable or disposable parameters. Ideally, the model should then yield
output values which can be compared to trusted experimental data. Unfortu-
nately, required data is commonly not available, unreliable, or determined for
inappropriate conditions. Disagreement between calculated (model) and
measured values can, however, provide a template for required measurements or
theoretical calculations.
Unfortunately, models and calculations can be developed and performed on a
time scale which cannot be matched by experimental determinations. This
commonly leads to the “over-extension” of models beyond validation, either by
comparison to measurements or by theoretical calculations. This is generally the
reason for the use of adjustable parameters. The more such parameters are
included the more over-extended and unreliable the model becomes. Such over-
extensions should be minimized by the iterative process of the model (oen
sensitivity) calculations, experimental determinations, model redevelopment.
Alison Davenport asked: Could you give further details on the uncertainty in
the input parameters to the model, and to the sensitivity of the model to different
parameters? Are there any input parameters for which improved measurements
would be helpful to reduce the uncertainty in the model?
David Shoesmith responded: There are many uncertainties in the input

parameters to the model in its present form. The mechanistic basis is reasonably
well established although a detailed understanding of how hydrogen peroxide
reacts and interacts with hydrogen on the UO2 surface has proven elusive. The key
uncertainties are in the values of the rate constants required, many of which are
uncertain and some of which are unknown. The sources and uncertainties of the
input parameters have been discussed elsewhere.1–3
The key uncertainty encountered is in the justication that parameter values
measured in experimentally accessible concentration ranges can be used in the
concentration ranges anticipated inside a failed container which are orders of
magnitude lower. Additionally the model cannot be considered fully developed in
its present form. While the goal is to develop a transparent and readily compre-
hensible model with as few complexities as possible, a number of features remain
to be elucidated. These include the possibility of corrosion product deposition,
especially within fuel fractures. Their presence will lead to uncertain diffusion

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elds between the two corrosion fronts within the container. The consequences of
various failure modes of the fuel cladding is also not included. Model validation is
also an on-going issue, and an attempt to compare model calculations to natural
analogs is being made.
1 L. Wu, Y. Beauregard, Z. Qin, S. Rohani and D. W. Shoesmith, Corros. Sci., 2012, 61, 83–91.
2 Linda Wu, Zack Qin and David W. Shoesmith, Corros. Sci., 2014, 84, 85–95.
3 Linda Wu, Nazhen Liu, Zack Qin and David W. Shoesmith, J. Electrochem. Soc., 2014, 161,
E3259–E3266.
Christopher Taylor asked: Early in the presentation you mention the hypoth-
esis or expectation that the epsilon particles, being noble, could drive anodic
processes by acting as a cathodic electron sink by catalyzing HER. However, it
appears that instead, your expectation is that they will have an opposite effect, by
quenching H2O2. Is this the correct interpretation of the role of epsilon particles,
or does the competition between these two effects still need to be elucidated?
David Shoesmith responded: We are studying these reactions extensively and

many features remain to be elucidated. We have good experimental evidence that
these particles act as cathodes to reduce hydrogen peroxide (in the absence of
hydrogen), as anodes to oxidize hydrogen (in the absence of hydrogen peroxide),
and as a catalysts on which hydrogen oxidation and hydrogen peroxide reduction
can couple to yield water. It is this last reaction which can consume hydrogen
peroxide and prevent it from driving uranium dioxide corrosion. To date we have
not been able to quantitatively determine the kinetic relationships describing
these reactions although we have some preliminary data. There are a number of
unresolved issues. We do not know the kinetics of hydrogen peroxide decompo-
sition (to oxygen and water) which model sensitivity calculations tell us are
important. The inuence of alpha radiolysis in “hidden” locations (deep cracks,
grain boundary tunnels) is underway but incomplete, and the relative importance
of the noble metal particles and the uranium dioxide surface in hydrogen
peroxide reactions is uncertain. I could extend the list!
Ross Springell said: You mention in your article that UO2 has the potential to
have a catalytic effect that may inuence its corrosion. Could you expand on this
point and describe how important the stoichiometry is in this aspect?
David Shoesmith replied: Many oxide catalysts act as electron donor–acceptor

catalysts especially p-type oxides.1 This is attributed to the existence of adjacent
metal ions with the surface ion being in a higher oxidation state (e.g., U(V)) than
that immediately below (U(IV)). This kind of catalysis is exhibited by Ce (III/IV)
oxide. If such a catalysis occurs then an increase in non-stoichiometry (x in
UO(2+x)) would be expected to enhance catalysis. This effect has been proposed to
explain the kinetics of hydrogen peroxide reduction on uranium dioxide.2,3
However, it is a little more complicated than this and presently not totally
resolved.
1 V. Presnov and A. M. Trunov, Elektrokhimiya, 1975, 11, 77.

2 J. S. Goldik et al., Electrochim. Acta, 2004, 49 1699.
3 J. S. Goldik, J. J. Noël and D.W. Shoesmith, J. Electroanal. Chem., 582, 2005, 241.

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Angus Cook commented: In your model system of a failed nuclear waste
container (Fig. 2) there is no accounting for any cladding material around the
nuclear fuel.
How might cladding change this system?
David Shoesmith answered: Only the electrochemical and chemical reactions

were included in the model presented. The Zircaloy cladding is expected to be
chemically inert and not involved in the redox processes determining the UO2
behaviour. Its effect will be as a separating barrier between the site of radiolytic
oxidant production at the fuel surface and the site of Fe(II) and H2 production at
the steel container inner surface. It will, therefore, inuence the diffusion
processes and hence the ability of H2 to control the redox conditions at the fuel
surface by reaction with H2O2 and of Fe(II) to consume H2O2 by the Fenton
reaction. Its efficiency in interfering with these reactions will be determined by

the physical nature of the failure in the fuel cladding. We are presently trying to
model this effect within our nite element model.
Dirk Engelberg said: With the presence of hydrogen peroxide in the aqueous
phase, and/or catalytic reactions expected to occur at the uranium surface/parti-
cles (H2/H+) wouldn't you expect the formation of uranium hydride?
David Shoesmith answered: The fuel form is uranium dioxide not uranium
metal. Hydride formation would only be expected if uranium in the zero oxidation
state was present. While H atoms will form on the noble metal particles (an alloy
of Ru, Pd and Mo), and some minor absorption into the particle may be possible,
this will not lead to reduction of the U(IV) oxide to U metal.
Christopher Taylor remarked: For the water gas shi and reverse water gas
shi research efforts, bifunctional catalysts that contain nanoparticles of precious
or noble metals dispersed over a redox-active oxide, like ceria, are used to tune the
reaction chemistry for CO2 + H2 # CO + H2O and potentially form hydrocarbon
products. In your case, you have a similar set-up between these epsilon particles,
which are noble and catalytic, and the redox active UO2. By analogy, then we
might expect the interfaces between the particles and the urania to be the active
regions whereby CO2 is able to engage in chemistry with the material. Are there
other possible insights that could be gained by this analogy?
David Shoesmith responded: The analogy is a good one. In the reaction you
describe on ceria you note that the whole oxide matrix is involved not just the
dispersed noble metal nanoparticles, but you suspect the coupling within the
uranium dioxide will be limited to regions close to the noble metal particles. I
agree. The area of the reactive uranium dioxide inuenced by the noble metal
anode/cathode will be determined by the electrical conductivity of the rare earth
doped oxide lattice and the ionic conductivity of the electrolyte it is exposed to;
i.e., this is a normal microgalvanic (or internal) coupling process.
I think the analogy can be extended in terms of the behaviour of the uranium
and cerium oxides. The hydrogen peroxide we are interested in will react directly
on the uranium dioxide surface besides via the galvanic coupling process, making
the catalytic properties of the oxide also important. Both cerium oxide and

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uranium dioxide have the same lattice structure and uranium dioxide has the
potential to act as a redox catalyst via similar mechanisms to those occurring on
the much more extensively studied cerium oxide. It is well worth investigating
whether this is the case and whether the tuning mechanisms for ceria that you
refer to also occur on uranium dioxide.
Clara Wren opened a general discussion of the paper by Ross Springell: The
concentration of the radiolytically-produced H2O2 that you quoted is very high at ~
104 M. What was the energy absorbed by water? Can X-ray induced radiolysis
create that high an H2O2 concentration? The photoelectrons generated in the UO2
matrix should lose most of their energy to overcome the binding energy and work
function, and, when they are ejected from the UO2 matrix, will have a relatively
low energy, on the order of ~ 100 eV. This is not sufficient to penetrate the
adsorbed water layer but is sufficient to ionize water molecules close to the UO2
surface, affecting the water chemistry close to the surface. If this is the case, the
X-ray induced corrosion may be different from that driven by higher energy
radiation such as gamma-rays. Can you comment on the potential differences
arising in X-ray and g-ray induced corrosion?
Ross Springell replied: The X-ray energy is 17 keV and for the average 0.5 mm
coverage of water that we used in this experiment, the transmission was 59%,
which means that 41% of the total photon ux (approx. 1012 photons s1) was
absorbed in the beam track through the water. By using the linear energy transfer
(LET) of X-rays at this energy it is possible to calculate the number of H2O2
molecules produced per 100 eV deposited, per photon. The high photon ux
results in the increase of H2O2 concentration up to its equilibrium concentration
within a fraction of a second. Both the X-rays and gamma rays have a similar LET
and produce similar proportions of radiolytic product, but it is certainly the
situation that the absorption in the water is much stronger for the X-ray case. In
fact, it is this property that we rely on to enable us to measure the corrosion in situ
during the time frame of a synchrotron experiment; in real spent fuel stores the
rates of corrosion are considerably slower.
Geoffrey Thornton stated: We have recorded SXRD data (CTR's) from a water/
TiO2(110) interface using ID32 at the ESRF. The photon ux was also 17 keV, with
a photon ux of 1012 ph s1. We see an interface ordered on the atomic scale. In
other words, there is no evidence of beam damage. A key difference between your
sample and the TiO2(110) substrate is that the former employs an insulating
substrate, whereas the latter was a self-doped n-type semiconductor. Hence, it
may be a charging effect that gives rise to the beam damage you observe.
Ross Springell answered: The beam parameters described in the SXRD

measurements on TiO2 at ID32 are remarkably similar to our own, and it's
surprising that no beam damage is observed at all. The possible charging of the
YSZ insulating substrates as a potential cause of the increased rate of corrosion
observed in the UO2 lms is a good suggestion and we will look toward a con-
ducting substrate system in the future to test this theory.

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Rob Lindsay commented: As you indicate in the paper, it is somewhat
surprising that the (001), (110), and (111) UO2 surfaces all exhibit similar disso-
lution rates. How well characterised are these surfaces? For example, have you
employed STM to image them in real space? It may be that dissolution is domi-
nated by loss of atoms from step edges or other ‘defect sites,' and so rates are
more similar than expected for the three surface orientations.
Ross Springell responded: To date our characterisation of the different

surfaces has relied solely on X-ray diffraction techniques and in some cases high
speed AFM. Diffraction spectra imply large regions with very low roughness (less
than 2 monolayers), but in order to be certain of the surface morphology we will
look to try a technique with much better real space resolution such as STM, as
suggested. In order to further investigate the effect of crystal surface, we are
planning an in situ high speed AFM study of the corrosion of a number of UO2
crystal grains on a longer time-scale, using hydrogen peroxide as the oxidant.
David Shoesmith asked: Have you tried to characterize the UO2 layer before
exposure and the oxidized surface layer aer exposure using techniques such as
Raman spectroscopy and X-ray photoelectron spectroscopy?
Ross Springell responded: We have made some measurements of the oxidised

surface layer aer exposure, using X-ray photoelectron spectroscopy (XPS),
mapping across a corroded region. Our rst results indicate a more oxidised
hyperstoichiometric surface into the corroded region and then potentially a
higher uranium oxide in the very centre of the trough, due to redeposition of
material out of the water, on drying. We have beam-time scheduled at I09, Dia-
mond Light Source, to conduct a full investigation of the oxidation of these
corroded regions in situ, using XPS. Raman spectroscopy is an excellent sugges-
tion; although our lms are too thin for this technique to be sensitive in this case,
we plan to grow a series of much thicker lms and measure the Raman spectra for
a range of stoichiometries.
Philippe Marcus asked: Can we really implant in the human body a stent that
would produce a lot of hydrogen? What is the conclusion in terms of the effect of
iron impurity in magnesium on hydrogen evolution (one of the hypotheses
included in the Introductory Lecture presented by Gerald Frankel1 to explain the
“anodic” hydrogen) and what are the implications for the application of Mg alloys
for stents (requested purity of Mg)?
1 G. S. Frankel, S. Fajardo and B. M. Lynch, Faraday Discuss., 2015, DOI:10.1039/c5fd00066a.
Sannakaisa Virtanen replied: Certainly the hydrogen gas evolution by Mg

based stents is of high concern. There are studies related to the fate of hydrogen
gas in different types of in vivo situations. The danger of hydrogen gas generation
in the biomedical application can be expected to depend on the temporal and
spatial rate of its production: i.e., sufficiently slow gas generation can be tolerated
(gas can be transported away and local build-up of signicant volumes of gas can
be avoided). What is typically observed for Mg alloys in simulated in vivo condi-
tions, for instance in cell culture medium (but NOT in more simple simulated

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body solutions, SBFs, which only mimic the inorganic components of blood and
do not contain for instance amino acids), is that the initial production of
hydrogen gas is quite strong, and in a relatively short time (in the rst hours of
immersion) the surface is “passivated” by formation of a protective corrosion
product layer. Therefore, the key for a safe application from my point of view is to
modify the alloy surface with a biodegradable coating, which only offers a weak
barrier function, but reduces the initially too high reactivity of the Mg surface.
Also, Mg alloy purity certainly is of very high importance in this eld.
The corrosion challenge is not only related to hydrogen gas. Also local pH
increase can be deleterious for the biological surroundings. But one should
consider that most laboratory studies on Mg corrosion are performed under static
conditions and this is far from the highly dynamic situation in vivo. So there is
quite a lot still to do.
Geraint Williams responded: This point is well made. The majority of research
devoted to bioresorbable Mg implants largely ignores the fact there may be
problems which arise in vivo due to high local concentrations of hydrogen caused
by corroding magnesium. Most attention has been concentrated on the
biocompatibility of the cations which are released upon corrosion. Given the well
documented inuence of iron impurity level on corrosion rate, closely controlling
the trace Fe content of Mg may provide a means of “tuning” the corrosion rate to
one which lies in an acceptable time window for optimum in vivo performance.
However, in reality the situation will be much more complicated since it is likely
that nominally pure Mg, with a certain “tuned” Fe trace content, may not possess
the requisite mechanical strength (e.g. for stent applications), and would need to
be alloyed with other elements. There may, in turn, be some interplay of these
additional alloying elements with Fe, which could either mitigate (e.g. Zr, Al–Mn)
or enhance (e.g. Si) the inuence of Fe on corrosion rate. As a result, there are
probably more straightforward methods of limiting corrosion rates, such as the
use of an appropriate biocompatible surface treatment or coating.
Stuart Lyon remarked: Should we be much more concerned with the inuence
of “low” or trace concentrations of elements in alloys and their inuence on the
surface structure/chemistry and corrosion?
John Scully replied: As mentioned in the closing lecture,1 I believe that trace
and minor alloying element effects are both one of the great triumphs of the
corrosion metallurgy eld and one of its least well understood aspects.
Consider the effects of Mo and nitrogen on stainless steels as well as Mo and W
on Ni–Cr alloys. Consider minor and trace elements effects on corrosion in copper
base alloys. Consider the effects of Cu and Ni or others in weathering steels. In the
case of amorphous alloys, minor alloying additions are oen made to improve
quench rate and glass formation but effects on corrosion are not well understood.
The need for understanding intensies further in high entropy alloys.
These effects are not well understood yet provide some of the most productive
area of technological accomplishments in corrosion metallurgy. Therefore, I see
some of these topics as very worthy for investigation as corrosion science looks
towards the future.

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1 John R. Scully, Faraday Discuss., 2015, DOI:10.1039/c5fd00075k.
Roger Newman responded: For the arsenic effect on dezincication, its

possible analogs, and for the startling detrimental effects of elements like N and P
on SCC of austenitic stainless steels (Tsujikawa), yes! By the way, the latter work is
still little-known outside Japan. For pitting, and stability of passivity generally,
probably not, at those very low levels. An exception is the “anodic segregation” of
sulfur studied by Marcus, where the S concentration rises to monolayer levels at
the metal-lm interface during passivation in acid. He also proposed that similar
segregation of N, in stainless steels containing that element, was responsible for
resistance to pitting – I would differ on that point, having shown that N markedly
reduces the dissolution kinetics in pit-like environments.
Weathering steels are another topic. Those levels are not really “trace” though.
In the magnesium world, because everything else “anodically segregates”, this is

an important topic.
David Shoesmith responded: Yes we should. Their inuence is particularly

noticeable in the light metal alloys (Mg, Al, Ti) as clearly noted in the introductory
address by Frankel1 and the presentations on Mg alloys. The possible inuence of
Fe impurities on the anodic formation of hydrogen is not the only example of an
“extreme” effect of apparently atomically-distributed impurities. The propagation
of crevice corrosion on titanium alloys varies considerably as the minor content of
Fe varies.
1 G. S. Frankel, S. Fajardo and B. M. Lynch, Faraday Discuss., 2015, DOI:10.1039/c5fd00066a.
Simon Gibbon communicated: Listening to the discussion today I could

believe that there is a real disconnect between the need to do highly dened
empirical work and the need to solve less well dened real alloy corrosion
problems – there is little connection to modelling. Is this really the state of
corrosion science today?
James Sullivan communicated in reply: I would agree that there is probably

quite a disconnect between the two and as discussed by Prof. Scully in his
Concluding remarks,1 there needs to be a collective effort by the community to
bring these areas closer together in the future. This may enable us to solve and
critically predict some of the complex corrosion behaviours of new and current
alloys.
1 John R. Scully, Faraday Discuss., 2015, DOI:10.1039/c5fd00075k.
Simon Gibbon communicated: High throughput experimentation and the

access to the ability to make a wider range of alloy compositions than could ever
be achieved manually, gives an incredible advantage in the search for sweet spots
of corrosion resistance, but it is not fundamentally different from Edison's
experiments to optimise the light bulb lament, only faster. Surely I must be
missing some good examples where modelling has made/is making an explicit
quantiable contribution to overcoming signicant corrosion issues?

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John Scully communicated in reply: I think that high throughput experiments
with higher delity data acquisition are certainly an opportunity to advance
corrosion technology. However, I agree with the notion of “sweet spots” in many
corrosion phenomena which means that a more targeted approach is required
where experiments are clustered around potential sweet spots instead of massive
testing of a wide range of alloy or coating compositions, for instance. As we all
know, the corrosion eld is full of examples where strong “thresholds” are seen.
The challenge is to nd and understand them.
One of the advantages of computational modeling is the ability, if the essence
of the corrosion phenomenon is captured in the model, to exercise the model over
many conditions to develop a better understanding of what factors really matter.
Then these factors can be focused upon in more limited and focused experiments.
This is different than the view you express above and in my opinion is not
Edisonian.
Regarding ICCME (Computational Corrosion Materials Eng), the success
stories are limited and in isolation but include tunable Al-TM-RE glass and
nanocrystalline coatings that our group invented,1–4 ultra high strength stainless
steels that do not require heavy metal coatings (Questek), and iron based BMG
which, maybe by accident, combine all the tools in the MSE tool box to make very
corrosion resistant materials (signicant Cr and Mo in solid solution, benecial
minor alloying elements such as C, B, Y, lack of inclusions or large defects etc.).
Another example might be grain boundary engineering of polycrystalline alloys
for SCC resistance. These examples stand in isolation and do not yet signal a
broad movement.
1 N. R. Tailleart, B. Gauthier, S. Eidelman and J. R. Scully, Metallurgical and physical factors

controlling the multi-functional corrosion properties of pulsed thermal-sprayed Al–Co–Ce
coatings, Corrosion, 2012, 68(3), 035006-1–035006-26.
2 J. R. Scully, F. Presuel-Moreno, M. Goldman, R. G. Kelly and N. Tailleart, User-selectable
barrier, sacricial anode, and active corrosion inhibiting properties of Al–Co–Ce alloys for
coating applications, Corrosion, 2008, 64(3), 210–229.
3 M. A. Jakab and J. R. Scully, On-demand release of corrosion-inhibiting ions from amor-
phous Al–Co–Ce Alloys, Nat. Mater., 2005, 4(9), 667–670.
4 F. Presuel-Moreno, M. A. Jakab, N. Tailleart, M. Goldman and J. R. Scully, Corrosion-
resistant metallic coatings, Mater. Today, 2008, 11(10), 14–23.
Janine Mauzeroll communicated in reply: On the atomic scale, ab initio and

DFT based models have been used to understand already known corrosion
inhibition, but also to predict the effect of doping. For example, models were used
to study the effect of chloride ions on passive NiO lms,1 the bonding of benzo-
triazole corrosion inhibitor on copper and copper oxide surfaces2 and the effect of
different doping elements on the thermodynamic corrosion properties of Ni
based alloys.3 The earlier has inspired much more research and interaction
between modeling and experiments on passive lms and their decomposition.4
Increasing scale size to microscopic phases in alloys and their coupling, models
are still being developed. One oen cited work in this eld is by Kiran Deshpande5
on the Microgalvanic coupling of alpha and beta phase in AZ91 magnesium
alloys.
Most direct impact has nite element modeling of macro galvanic corrosion.
Frequently used in engineering applications to estimate the effect of galvanic

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coupling are numerical models based on the ionic conductivity of the electrolyte,
i.e. the Laplace equation of the electric eld.6–8
1 Asmae Bouzoubaa, Boubakar Diawara, Vincent Maurice, Christian Minot and Philippe
Marcus, Corros. Sci., 2009, 51, 2174–2182.
2 Anton Kokalj, Faraday Discuss., 2015, DOI:10.1039/c4fd00257a.
3 Bai-Lin Lü, Guo-Qing Chen, Wen-Long Zhou, Hui Su and Rui Liu, J. Nucl. Mater., 2011,
286–291.
4 Toni Massoud, Vincent Maurice, Lorena H. Klein and Philippe Marcus, J. Electrochem. Soc.,
2012, 160, C232–238.
5 Kiran B. Deshpande, Electrochim. Acta, 2011, 56, 1737–1745.
6 Nicolas Murera, Roland Oltra, Bruno Vuillemin and Olivier Néel, Corros. Sci., 52, 130–139.
7 Dao Trinh, Philippe Dauphin Ducharme, Ushula Mengesha Tefashe, Joseph R. Kish and
Janine Mauzeroll, Anal. Chem., 2012, 84, 9899–9906.
8 Daniel Höche, J. Electrochem. Soc., 2015, 162, C1–C11.
Christopher Taylor opened a general discussion of the paper by Geraint Wil-

liams: As I understand your interpretation of the Mg corrosion, at higher
concentrations of NaCl, you expect that the solution can support a higher
throwing power, and so the radial growth of the corrosion front occurs, whereas in
lower concentrations of NaCl, the throwing power is lower, thus only 1-D
spreading of corrosion occurs, giving this liform appearance. Is this process
amenable to modeling? It is not clear to me how changing the throwing paper
should lead to a shi in geometry, only in rate, so I would nd a mathematical
model convincing. Can you describe how the geometry of the corrosion front
changes in the intermediate case, as one moves from higher concentration
(radial) to lower concentration (1D)?
Geraint Williams responded: I would be more than happy to see the

phenomenon modelled and willing to supply the relevant experimental data to
any volunteer who felt like taking on such an endeavour. For the intermediate
case (between 0.1 M and 0.01 M NaCl), the breakdown of the Mg surface causes
initial propagation of circular features, but as they grow radially, the anodic
region at their perimeters starts to fragment. Consequently, liform-like tracks
emanate from these points of fragmentation, as shown in the photograph (see
Fig. 1) of a post-corrosion Mg surface aer immersion in 0.02 M NaCl (aq), and
disc-like corrosion propagation stops.
Alison Davenport asked: The growth velocity of the corrosion laments can be
converted into a current density. Could you comment on the range of current
density values found, and in particular if there is a minimum current density
below which lament growth cannot take place?
Geraint Williams answered: Yes it is correct that velocity can be converted to a

current density value, although this requires some assumptions to be made
regarding the depth of anodic dissolution and the width of individual laments.
In a previous paper,1 a more rigorous characterisation of liform corrosion
affecting the same type of Mg under similar chloride ion concentrations was
described. In this work the minimum lament width observed was 0.1 mm and a
depth of attack of ca. 1 mm was estimated by AFM mapping. Using an average
lament velocity of 1 mm s1 and assuming the front of the “track” comprises a 3
dimensional rectangle of width 0.1 mm, length 103 mm and depth 103 mm,

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Fig. 1 Photograph of a post-corrosion Mg surface after immersion in 0.02 M NaCl (aq).
then it can be calculated that a mass of Mg equating to 1.8 1010 g is excavated

every second (using density (Mg) ¼ 1.8 g cm3). Using Faraday’s law this works out
as a current of 1.4 mA and if it is further assumed that the area from which it
emerges comprises the rectangle face (width 0.1 mm, length 103 mm), then the
current density becomes 14 A m2. Given that lament velocity values never fall
below 0.7–0.8 mm s1 and that the minimum width is ca. 0.1 mm, then it appears
that current density values of at least 10 A m2 are required to sustain propaga-
tion. This correlates well with SVET-derived anode current density values of
between +5 and +15 A m2 reported in the aforementioned publication.
1 G. Williams and R. Grace, Electrochim. Acta, 2011, 56 1894.
Gerald Frankel asked: It seems that you should be able to understand the
phenomenon by assessing the cathodic activation aer corrosion using polari-
zation curves. This might vary with the chloride concentration similar to the effect
of the prior applied anodic current density. In that case, the corrosion
morphology might be controlled by the amount of available cathodic current and
galvanic coupling rather than by the ohmic resistance.
Geraint Williams responded: Yes, this is certainly a possibility that should be

considered. However, there will be some difficulty in reproducibly generating a
working electrode area which is fully corroded, especially where liform attack is
prevalent and there will be some “islands” of uncorroded surface remaining
amongst the network of dark tracks, even aer protracted immersion. Also, there
may be some issues in effectively accounting for iR drops in carrying out poten-
tiodynamic experiments on fully corroded surfaces over a range of different
chloride concentrations, even in the presence of a Luggin capillary. One would
also have to think of a physical description of why chloride ion concentration
would inuence the electrocatalytic efficiency of the corroded surface toward
cathodic hydrogen evolution.

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David Shoesmith asked: You elegantly demonstrate the relationship between
anodes and cathodes and show how corrosion tracks across the surface. Is the
substrate microstructure at all involved in determining the direction of
propagation?
Geraint Williams responded: There is no real indication, especially at

concentrations of 0.1 M NaCl (aq) and above, that propagation is inuenced by
microstructure for the pure Mg studied here. There are reports in the literature,1
that indicate liform corrosion (FFC) on pure Mg can preferentially follow certain
crystallographic features of the Mg grains. These authors showed that direc-
tionality of individual laments appeared to be inuenced by changes in orien-
tation at grain and twin boundaries. However, the investigation was carried out in
chromate inhibited dilute chloride electrolyte, which is not the case for the
present work disseminated in this Faraday discussion. The random walk FFC
patterns observed upon immersion in 0.01 M electrolyte (see Fig. 1c), for the
rather impure form of Mg studied in our work, suggests that microstructural
inuence on lament directionality is minimal in the absence of dissolved
chromate inhibitor.
1 P. Schmutz, V. Guillaumin, R. S. Lillard, J. A. Lillard and G. S. Frankel, J. Electrochem. Soc.,

2003, 150, B99.
Clara Wren opened a general discussion of the paper by Janine Mauzeroll:

Your sensors use microcapillaries for local corrosion potential measurements. Mg
corrodes very fast and, as far as I can tell, this corrosion is oen limited by the
solution transport rate. Do you expect the same solution transport behaviour for
redox species in the microcapillaries and in bulk water? How do you ensure that
what you are measuring is not the transport limited corrosion potential inside the
microcapillary?
Janine Mauzeroll answered: The question is referring to the measurement of

corrosion potential of the different microstructures using the microcapillary
technique presented in Figure 1 of our paper. For this measurement, the
meniscus of the lled micropipette is brought in electrical contact with the
substrate where the open circuit potential is recorded. This experiment does not
consist of any measurement of substrate kinetics and we do not extract any rate
information where solution transport is important, as previously mentioned.1
When performing a substrate polarization curve, we assume that the mass
transport within the micropipette will be governed by diffusion only within the
connes of the micropipette. The comparison of numerical simulations for mass
transport governed by diffusion only within micropipettes (~500 nm) is in excel-
lent agreement with experimental data.2
1 S. Thomas and H. Bohni, Analytical Methods in Corrosion Science and Engineering. CRC
Press, Boca Raton, FL, USA, 2005, pp. 649–696.
2 Williams et al., Anal. Chem., 2009, 81, 2486–2495.
David Williams remarked: The shear force-controlled scanning vibrating

capillary seems a very powerful general tool to me, analogous to the SNOM. I
wonder what other probe methods you have considered that might utilise this

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platform – for example scanning ion conductance microscopy to map solution
conductivity changes or using the capillary as a waveguide to implement optical
microscopy or perhaps Raman. I wonder also if the modulation of the signal
caused by the vibration could be used to advantage.
Janine Mauzeroll answered: The shear force controlled scanning vibrating

capillary can be adapted for many situations in corrosion science simply by
changing the nature of the probe.
In its unmodied state, the scanning droplet cell remains versatile towards
electrochemical techniques that can be performed locally such as potentiody-
namic polarization or voltammetry to extract local kinetics through accurate
corrosion modeling. The wide variety of electrochemical techniques also include,
local chronoamperometry that can probe ions released during the corrosion
process1,2 or even perform local modication of surfaces.3,4

It can be easily adapted to measure local impedances, making it very useful in
the study of ageing and failure of protective coatings.5–8
It can be adapted to quantify several chemical uxes generated during the
corrosion. For example, corrosion product deposition affects the SECM feedback
regeneration of different dissolved redox mediators such as FcMeOH when an
alloy is immersed in a corroding solution.9 It can also be used to directly track
hydrogen uxes from the alloy microstructure.10 It can also be modied through
the use of an ion-selective microelectrode to track Mg2+ uxes.11 Finally, with
minor microelectrode manipulations, it is possible to pull ber optics and to
monitor combined spectroscopy and electrochemistry as reported by A. J. Bard in
the early 2000s.12 I cannot conclusively comment on if the modulation of the
signal caused by the vibration could be used to advantage.
1 K. A. Lill, A. W. Hassel, G. Frommeyer and M. Stratmann, Electrochim. Acta, 2005, 51, 978–
983
2 M. M. Mennucci, M. Sanchez-Moreno, I. V. Aoki, M. C. Bernard, H. G. Melo, S. Joiret, and
V. Vivier, J. Solid State Electrochem., 2012, 16, 109–116.
3 M. M. Lohrengel, A. Moehring and M. Pilaski, Fresenius’ J. Anal. Chem., 2000, 367, 334–339.
4 M. Pilaski and M. M. Lohrengel, Electrochim. Acta, 2003, 48, 1309–1313.
5 F. Zou and D. Thierry, Electrochim. Acta, 1997, 42, 3293–3301.
6 D. Snihirova, L. Liphardt, G. Grundmeier and F. Montemor, J. Solid State Electrochem.,
2013, 17, 2183–2192.
7 A. M. Mierisch and S. R. Taylor, J. Electrochem. Soc., 2003, 150, B303–B308.
8 M. W. Wittmann, R. B.Leggat, S. R. Taylor, J. Electrochem. Soc., 1999, 146, 4071–4075.
9 W. Liu, F. Cao, Y. Xia, L. Chang and J. Zhang, Electrochim. Acta, 2014, 132, 377–388.
10 U. M.Tefashe, M. E. Snowden, P. Dauphin-Ducharme, M. Danaie, G. A. Botton and
J. Mauzeroll, J. Electroanal. Chem., 2014, 720–721, 121–127.
11 P Dauphin Ducharme, R. M. Asmussen, D. W. Shoesmith and J. Mauzeroll, In situ Mg2+
release monitored during magnesium alloy corrosion, J. Electroanal. Chem., 2015, 736,
61–68.
12 Y. Lee, S. Amemiya and A. J. Bard, Scanning electrochemical microscopy. 41. Theory and
characterization of ring electrodes, Anal. Chem., 2001, 73, 2261–2267.
Stuart Lyon opened a general discussion of the paper by Sannakaisa Virtanen:

Given the low net atomic number of Mg-based implant alloys, how can they be
easily imaged by X-rays?
Sannakaisa Virtanen answered: They cannot be easily imaged by X-rays. So I

assume one would try to use some X-ray markers. In the case of coated Mg-based

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implants, the coating could provide also a means for imaging. I am not aware if
there is a state-of-the-art in the eld, or simply some exploratory approach.
Rob Lindsay said: From reading your paper, I believe you have assumed a
homogenous substrate for quantication of the XPS data. Clearly, if this is true,
this substrate model does not represent reality particularly well, in my opinion, as
there will be discrete layers of material, with the metallic substrates lower most.
How do think your approach impacts upon your interpretation of the XPS data
(e.g. data shown in Fig. 8)?
Sannakaisa Virtanen replied: The XPS data presented simply shows the at%
determined, and is not further interpreted for instance in view of a homogeneous
or partial coverage or in view of the different layers from the metallic substrate, to
passive lm, to the protein adsorption layer. We do not believe that we have a well-
ordered and complete monolayer of albumin in this case. The XPS data should be
considered only in a qualitative manner, i.e. in comparison of the different
systems (substrate material, time, electrolyte). In order to perform a full analysis,
more experimental data would be required, including information on coverage
and thickness of the different layers.
Kirsi Yliniemi remarked: In addition to the nature of surface charges on either

Mg or Fe surfaces, could you comment how the surface charge density affects the
protein adsorption as it may also inuence your results? There exist models which
suggest that at low surface charge densities polyelectrolytes adsorb on a more at
orientation (2D lms) while at higher surface charge densities thicker 3D lm
starts to grow (see for example the review1).
1 A. Dobrynin and M. Rubinstein, Prog. Polym. Sci., 2005, 30 1049–1118.
Sannakaisa Virtanen replied: Thank you very much for the important
comment and helpful literature. Yes, indeed not only the type of surface charge
but also the charge density should play a role. Until now, we did not carry out any
detailed studies on this, and the surface charge considerations in our paper are
simply based on IEP values found in the literature.
But indeed we would like to know more about the type of the protein
adsorption layers, so in addition to addressing the question on the amount of
protein adsorbed on different surfaces, we would like to study the orientation of
the proteins on the surface (with additional experiments and a more detailed data
analysis) and also their functionality (for instance, are they in their native
conformation or possibly denaturated, depending on the surface they are
adsorbing on).
In the case of Mg some of the studies we would like to do are challenged by the
high reactivity of the Mg surfaces in aqueous solutions, so we oen have the
problem of not only adsorption of proteins taking place but at the same time
substantial corrosion of the substrate (this is also briey mentioned in the paper).
Johannes Lützenkirchen communicated: I have a comment concerning the

remark in the introduction of the paper, where you mention that from your
references 14, and 19–27, “both acceleration and inhibition of corrosion has been

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observed” with respect to the action of proteins related to Mg-materials. Your
interpretation is based on the charging of the adsorbing surface and that of
dissolved protein. The opposite sign of charge should favor adsorption and cause
inhibition. In that respect you quoted from your reference 38 a compilation of
points of zero charge for Mg-related surfaces. Indeed the points of charge of
particles of these materials have been reported to be high (i.e. above pH 10), but a
scan of references 14, and 19–27 of your paper shows that usually at surfaces
have been used in the adsorption and corrosion studies. It has been previously
observed that such at surfaces may have points of zero charge that are much
lower than those of the corresponding particles.1–4 It is one issue we discuss in
our paper. Fig. 2 shows unpublished zeta-potential measurements for a at MgO
surface in 5 mM NaCl. The system has been titrated under puried and humied
Argon atmosphere, using HCl and NaOH solutions. We used freshly prepared
NaOH solution to exclude carbon dioxide. The MgO surface is expected to

hydroxylate and expose a Mg(OH)2 like surface to the solution. Even for this
“MgO”-surface, we retrieve a drastic difference between particles and at plates. It
has been shown that this feature also occurs on alumina specimens of different
orientation,2,3 so that it is not related to the surface chemistry.
The isoelectric point (IEP) of the sample was initially at pH 4 as shown in Fig. 2.
On aging the IEP increases, but remains below pH 5 (data not shown), i.e. still
much lower than the powder values from ref. 38 of our paper. It is important to
note that data on sapphire-c surfaces show that roughness decreases the IEP of
this plane to even lower values (Lützenkirchen et al., manuscript in preparation).
Furthermore, the wide variation of the IEPs in Kosmulski’s collection (ref. 38)
of many samples would make conclusions based on literature data alone arbitrary
for many cases. Thus the use of published particle IEPs does not necessarily give
an appropriate interpretation. Even for nominally identical solids, the IEP may
vary widely. Therefore, it is favorable to measure it for the conditions used. In
particular since adsorption of some proteins may occur even under electrostati-
cally unfavorable conditions.5 Although in the present case, no contradiction
occurs between the charge-interpretation and the experimental data, in general
the point of zero charge of a given sample should be determined to avoid
ambiguity.
Fig. 2 Zeta-potential of a flat MgO surface in 5 mM NaCl.

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A related question concerns the iron samples. Does the entry in Table 2 invoke
that ferrous iron is the relevant form of iron? The background of the question is
that, while ferric oxides, hydroxides and oxyhydroxides are easily studied and the
IEPs can usually be determined quite well, iron(II) oxide and hydroxide minerals
are much more difficult to investigate. One major difficulty is that it is crucial to
avoid oxidation of iron(II). Very few studies on these iron(II) systems are therefore
available and only recently it has been reported6 that the IEPs of most of the
iron(II) samples under investigation in that study exhibited IEPs of about 10 or
higher.6 The substrates also showed transformation phenomena. The data from
ref. 38 (in your paper) are all for pure iron(III) systems or magnetite. How would
the interpretation be affected if you considered the higher IEPs from the recent
study?6
1 G. V. Franks and Y. Gan, J. Am. Ceramic Soc., 2007, 90, 3373–3388.

2 G. V. Franks and L. Meagher, Colloid Surf. A-Physicochem. Eng. Asp., 2003, 214, 99–110.
3 J. P. Fitts, X. Shang, G. W. Flynn, T. F. Heinz and K. B. Eisenthal, J. Phys. Chem. B, 2005, 109,
7981–7986.
4 E. Ma ˛czka, J. Luetzenkirchen and M. Kosmulski, J. Colloid Interface Sci., 2013, 393, 228–
233.
5 T. Arai and W. Norde, Colloids Surf., 1990, 51, 1–15.
6 E. Maczka, E. Jartych and M. Kosmulski, Colloid Surf. A-Physicochem. Eng. Asp., 2014, 441,
326–330.
Sannakaisa Virtanen communicated in reply: Thank you for the very inter-
esting comments and questions and also for sharing some unpublished data. I
completely agree that our approach is a rough and simple one, as certainly the IEP
values should be measured for the sample surfaces under the conditions of the
study, to have a better and more realistic view. Also, I agree that surface charge is
not the only factor inuencing protein adsorption, for instance surface wettability
is also of importance. If other driving forces are stronger than electrostatic
interactions, then adsorption could take place as you mention also for electro-
statically unfavorable conditions. In our case, as both Fe and Mg surface are
hydrated and show a similar hydrophilic behaviour, according to the literature
electrostatic interactions can be more signicant.
As regards the nature of the Fe surface: The passive lm formed in NaOH
should be an oxide with a mixed valency between Fe3O4 and Fe2O3 (but not FeO).
We refer to the values for FeO/Fe(OH)2 in Table 2, as we assume a hydroxide
deposit layer on top of the Fe-oxide layer. Again, a determination of IEP values for
the given case should be carried out.
The discussion in the manuscript is based on the fact that our hypothesis on
the relevance of the surface charge argument seems to hold for two different
proteins. But it still remains a hypothesis.
Clara Wren opened a general discussion of the paper by James Sullivan: Your
corrosion rate decreases with the aluminium content in the alloy. Have you tried
to normalise the corrosion rate with respect to the same zinc–magnesium or
magnesium content? Is the change in corrosion rate simply a function of the
relative amount of magnesium available, or is there any synergistic effect of the
composition-induced alloy-microstructure on the corrosion rate?

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James Sullivan replied: We haven't tried to normalise the data to date but that
is an interesting suggestion. I think the ultimate change in corrosion rate of these
alloys is dependent on both alloy additions (Mg and Al) especially in atmospheric
corrosion conditions where the establishment of Al and Mg corrosion products
are critical for the performance of these alloys. I feel the initial corrosion rate
differences observed here maybe more dependent on increasing Al levels with a
greater coverage of alumina present as the eutectic volume fraction increases that
is more resistant to corrosion initiation in the earliest of stages.
Stuart Lyon asked: What is the specic composition of the various components
of the eutectic in these complex Zn–Al–Mg alloys? How does the area/volume
fraction of eutectic inuence the overall corrosion performance?
James Sullivan answered: We haven't performed a detailed experimental

analysis of the various phase compositions. MTDATA simulations were performed
for ZMA 2 during its development that suggested that the binary eutectic con-
tained MgZn2 and Zn lamellae with around 1% Al in the Zn lamellae and 0.6–0.8%
Al in the MgZn2. In the ternary eutectic the same phases were present with
addition of an Al fcc phase containing 66% Al, 0.02% Mg and the remainder Zn.
The volume fraction of eutectic and its inuence on corrosion performance are
given in the presented paper in Figures 3 and 7 and show a fairly linear rela-
tionship between increased corrosion performance with increasing eutectic
volume fraction.
Gerald Frankel said: Why doesn't the attack in the eutectic region go deep into
the structure and why does it initiate at only a few places and then spread across
the surface?
James Sullivan responded: The attack does also penetrate vertically into the
sample and we have seen this from examination of cut samples post corrosion
although it would seem that the rate of lateral spreading is greater. The reason for
the corrosion spreading through the eutectic laterally at the surface may be due to
the surface being more eutectic rich as the solidication sequence starts with
nucleation of Zn rich dendrites at the steel substrate. Therefore the volume
fraction of primary Zn is greater at the coating/steel interface with a subsequent
reduction of primary Zn and increase in eutectic as the coating is traversed to the
surface. As the MgZn2 in the eutectic is the preferential phase for initial corrosion
attack then lateral attack through this eutectic rich surface may dominate.
Arjan Mol asked: First, I would like to thank James Sullivan for presenting this
very interesting work and paper during this Faraday Discussions session, I greatly
enjoyed it. My question is the following: can you please show, explain and/or
comment on the positions and evolution of (local) cathodic and anodic areas in
the SVET measurements with time and their correspondence to those in the time-
lapse optical microscopy videos considering a.o. the different lateral resolutions
of the techniques?
James Sullivan responded: That is an interesting question. The SVET samples

are much larger, 10 10 mm compared with the 1mm diameter circle area of the

View Article Online
time lapse samples. The SVET has a practical resolution of around 150 microns.
On the SVET maps we see localised anodes that are well spaced apart (>1 mm) and
have a radius of approximately 500 microns. It must be remembered that this
reects the current ux from the anodic features that the SVET detects in its plane
of scan 100 microns above the sample surface. As the SVET scans progress the
anodic features actually spread out as small rings from the initiation point. I have
attached a movie to show this.† It is somewhat difficult to correlate this with the
time-lapse movies due to the differences in sample area and resolution of the
techniques but the spreading of the anodes as rings may reect the lateral growth
of the anodic features shown in the time-lapse videos. Obviously, the growth of
features in the time-lapse experiments maybe more constrained due to the
smaller sample area exposed.
Steven Street asked: The three different ZMA alloys had quite different
dendrite sizes, indicating different thermal gradients when solidifying. As
corrosion seemed to propagate in the interdendritic regions, is there any value in
trying to rene the size of these dendrites? Would this improve the corrosion
behaviour of these alloys?
James Sullivan responded: These experiments at a range of cooling rates were

carried out using a 1.6 wt% Mg 1.6 wt% Al ZMA alloy during the development
phase of this alloy and little difference was observed during industrial corrosion
tests. It would be interesting to see if any effects of morphology could be identied
using this technique. Within the group we have certainly seen that morphological
differences within the microstructure induced by cooling rate changes seem to
inuence the corrosion behaviour of Zn - 4.8 wt% Al alloys.1
1 J. Elvins, J. A. Spittle and D. A. Worsley, Corros. Eng., Sci. Technol., 2003, 197–204.
Stuart Lyon asked: Corrosion resistant metallic coatings on steel are much
thinner than they used to be. How does this inuence the corrosion process/
resistance at the cut edge?
James Sullivan answered: These ZMA coatings are certainly thinner than more
traditional HDG type coatings but in industrial salt spray tests they certainly
outperform the HDG materials during surface testing. We also see this
improvement in corrosion performance when examining surface corrosion. At the
cut edge we have comparable performance to that of HDG for the thinner ZMA
coating in SVET and external run-off testing that is encouraging considering the
change in anode/cathode ratio. However, the performance at the cut edge is not
nearly as improved as the surface performance in comparison to HDG, that may
reect this change in anode/cathode ratio.
Clara Wren remarked: What is the geometry of the viewing cell, the diameter
and the depth of the solution, with respect to that of the rest of the corrosion cell?
I noticed in your video images that the corrosion front always starts close to the
boundary between the viewing area and the rest of the corrosion cell. Could your
observation indicate that the Mg corrosion is solution transport limited?

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James Sullivan answered: The distance between the viewing window and the
sample is around 1 mm so there is a 1 mm body of electrolyte between the sample
and the window. The diameter of the protective shroud on the microscope is
20 mm. The total volume of electrolyte in the cell is 250 ml and electrolyte is
accessible to the sample from 360 from the bulk volume into the 1 mm gap as
shown in Figure 1 in the paper. The corrosion oen starts near the periphery of
the exposed area as the circular area is masked using Teon tape. The slight
geometry change near the tape is oen sufficient to induce anodic activity here
and we also see this fairly regularly in SVET experiments where again a sample
area is masked off using tape. We plan to carry out some tests involving stirring to
assess the effect on the corrosion mechanism and to assess if diffusion of species
is restricted into the gap above the sample but I feel with a 1 mm gap there maybe
sufficient space for electrolyte diffusion especially as it can access the sample
from the full circumference around the shroud.
David Williams commented: I'm interested in the patterns and timing of

appearance of the dark shadows that correspond to precipitation of the corrosion
products – for example the sudden appearance of a ring that fades and then
reappears. There seems to be some rich information here about the development
of the anodic and cathodic sites and convection–diffusion–reaction in the
immediate vicinity of the interface. Are you able to comment on this?
James Sullivan replied: I too feel that this is potentially showing some inter-
esting information about the nature of anodic and cathodic sites, the ionic
diffusion between the two electrodes and pH gradients established between them.
The pH effects have been demonstrated in some previous work1 using a
phenolphthalein indicator and is visible due to the dissolution of Mg corrosion
products as the front of anodic activity moves, presumably as the pH drops local
to the anodic site. I think it may also be interesting to see the effect of electrolyte
concentration on the formation of the corrosion product rings with regards to the
distance from the anode to assess the effect of the electrolyte's throwing power on
anode-cathode spacing.
1 James Sullivan, Shahin Mehraban and Jon Elvins, Corros. Sci., 2011, 53(6), 2208–2215.
Su-Ting Cheng said: In Fig. 2, the red area increases largely from ZMA1 to
ZMA3. Since the bulk concentrations of Zn (green) and Mg (red) are kept the
same, a different colour distribution could indicate a surface segregation of Mg.
Have you ever measured the concentration of elements throughout the whole
depth of the specimens? We have studied the Mg–Zn system with DFT, and the
results tell us the surface of the MgZn2 intermetallic compound is more stable
with a higher surface Mg concentration, either in vacuum or in contact with
oxygen. It would be nice to see if this could be also observed in experiments.
James Sullivan responded: I may have misunderstood the question but the
quantity of Mg increases from 1–3 wt% from ZMA 1–3 and the Zn level drops as
the Mg and Al levels increase. This I believe accounts for the increase in red as the
volume fraction of eutectic increases in the microstructure from ZMA 1–3. At
present we have not measured the depth prole of the elements.

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Rob Lindsay stated: I was wondering if you believe that the lamentous
precipitates you observe (as shown in Fig. 10 (B)) are important for controlling
corrosion or are just an interesting phenomenon?
James Sullivan replied: The laments are an interesting phenomenon but

I think they can offer an important role in controlling corrosion as the deposition
of the laments occludes the surface from further attack potentially. I think the
initial stages of precipitation local to the anodic features also demonstrates quite
nicely the formation of inhibitor lms at the anode. Also, these conditions may
reect those occurring in drying electrolyte lms where concentration of salts may
become saturated.
Simon Gibbon commented: Yesterday Mira Todorova1 told us about the

application of point defect models to give new insights into the defects formed on
zinc surface which could lead to corrosion. In your paper you have considered the
corrosion behaviour of commercially important zinc alloys. I would be interested
to know if you have considered applying such models to help in the under-
standing of your systems?
1 Mira Todorova and Jörg Neugebauer, Faraday Discuss., 2015, DOI:10.1039c/4fd00238e.
James Sullivan answered: This is not something we have considered to date but
it would be of interest to assess how the model could be applied to these alloys to
provide a prediction of corrosion behaviour with regards to preferential attack.
Trevor Hughes communicated: A very interesting paper on the use of in situ

time-lapse optical microscopy to compare the corrosion behaviour of Zn–Mg–Al
alloys in 1% NaCl at pH 7. In the paper it is stated “it may be counterintuitive that
an increased eutectic volume would reduce the corrosion rate given that these
phases are preferentially attacked in the microstructure but it would seem that
increased levels of Mg and Al in the alloy create more robust oxide layers due to
their rapidity of reaction and the passive nature of Al2O3.” Question 1: Have the
authors looked at brines with different pH, presumably the passive oxide layers
would not be stable in alkaline (pH 10–11) brines? What are the pH limits of such
passive oxide layers. In addition, for the neutral (pH 7) system, what is the effect of
elevated temperatures?
The paper also shows that the corrosion rate of the ZMA2 alloy (1% NaCl, pH 7)
decreases in the presence of sodium phosphate (0.0001, 0.01 mol L1 Figure 13).
Question 2: How does this response to phosphate compare for the 3 alloys studied
and for pure Zn?
James Sullivan communicated in reply: We are currently undertaking a matrix

of tests that include varying the pH with pH levels of 3, 7 and 10 coming under
examination. To date I cannot give a detailed report on the results as they are
fairly preliminary but the initial indications do indeed show visual differences to
the progression of corrosion and formation of corrosion products. We have not
carried out any tests as of yet at an elevated temperature and to date we have only
carried out the Phosphate tests on ZMA2. However, a pure Zn test is in the matrix
of tests planned.

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Faraday Discussions

Cite this: DOI: 10.1039/c5fd90046h

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Localised corrosion: general discussion†

Stuart Lyon, Rob Lindsay, Trevor Hughes, Johannes Lützenkirchen,

Philippe Marcus opened a general discussion of the paper by Roger Newman:

This journal is © The Royal Society of Chemistry 2015 Faraday Discuss.

1 H. W. Pickering, Corros. Sci., 1983, 23, 1107.

1 J. Luo, personal communication.

Faraday Discuss. This journal is © The Royal Society of Chemistry 2015

1 R. C. Newman, H. S. Isaacs and B. Alman, Eﬀects of sulfur compounds on the pitting

This journal is © The Royal Society of Chemistry 2015 Faraday Discuss.

Faraday Discuss. This journal is © The Royal Society of Chemistry 2015

Philippe Marcus answered: My response to this question is in three points:

This journal is © The Royal Society of Chemistry 2015 Faraday Discuss.

Faraday Discuss. This journal is © The Royal Society of Chemistry 2015

1 G. S. Frankel et al., J. Electrochem. Soc., 2014, 161(4), C195–C200.

Steven Street replied: Samples were in humidity controlled desiccators with

This journal is © The Royal Society of Chemistry 2015 Faraday Discuss.

Steven Street answered: Evans’ Droplet experiments on steel describe macro-

Faraday Discuss. This journal is © The Royal Society of Chemistry 2015

Steven Street responded: We don’t doubt the importance of sulphide inclu-

1 A. J. Davenport, L. Guo, N. Mi, H. Mohammed-Ali, S. M. Ghahari, S. R. Street, N. J. Laycock,

This journal is © The Royal Society of Chemistry 2015 Faraday Discuss.

Roger Newman commented: The reference to Evans' famous drop experiment

Faraday Discuss. This journal is © The Royal Society of Chemistry 2015

Siaw Foon Lee communicated: Under the section of “Experimental”, third

Steven Street communicated in reply: The concentration of the solution is

Steven Street communicated in reply: Chloride deposition density is an

Siaw Foon Lee communicated: Under the section of “Experimental,” subsec-

This journal is © The Royal Society of Chemistry 2015 Faraday Discuss.

Steven Street communicated in reply: Oxygen concentration was not measured

Dirk Engelberg opened a general discussion of the paper by V. Vivier: Do you

Stephane Heurtault answered: The proximity of the micro-capillary to the

Alison Davenport remarked: Have you carried out a systematic investigation to

Faraday Discuss. This journal is © The Royal Society of Chemistry 2015

Stephane Heurtault replied: We used such a strong sulfate concentration to be

1 N. Aouina et al., Electrochim. Acta, 2013, 104, 274.

1 G. S. Frankel, J. Electrochem. Soc., 1998, 145, 2186.

David Williams commented Laycock et al. have given a rather complete

This journal is © The Royal Society of Chemistry 2015 Faraday Discuss.

1 N. J. Laycock, S. P. White, J. S. Noh, P. T. Wilson and R. C. Newman, Perforated covers for

Stephane Heurtault responded: The Laycock model is a great advancement in

1 R. C. Newman and M. A. A. Ajjawi, Corros. Sci., 1986, 26, 1057.

Alison Davenport commented: We have recently carried out some radiography

Faraday Discuss. This journal is © The Royal Society of Chemistry 2015

Alison Davenport opened a general discussion of the paper by David Shoe-

David Shoesmith answered: A number of experimental approaches can be

1 M. Broczkowski et al., ACS Symposium Proc., 2010, 1046, 34–380.

This journal is © The Royal Society of Chemistry 2015 Faraday Discuss.

John Scully asked: Could you comment on the number of adjustable or

David Shoesmith responded: There are many uncertainties in the input

Faraday Discuss. This journal is © The Royal Society of Chemistry 2015

David Shoesmith responded: We are studying these reactions extensively and

David Shoesmith replied: Many oxide catalysts act as electron donor–acceptor

1 V. Presnov and A. M. Trunov, Elektrokhimiya, 1975, 11, 77.

This journal is © The Royal Society of Chemistry 2015 Faraday Discuss.

David Shoesmith answered: Only the electrochemical and chemical reactions

reaction. Its eﬃciency in interfering with these reactions will be determined by

Faraday Discuss. This journal is © The Royal Society of Chemistry 2015

Ross Springell answered: The beam parameters described in the SXRD

This journal is © The Royal Society of Chemistry 2015 Faraday Discuss.

Ross Springell responded: To date our characterisation of the diﬀerent